CN101328286B - Rubber composition, clinch, and tire - Google Patents
Rubber composition, clinch, and tire Download PDFInfo
- Publication number
- CN101328286B CN101328286B CN2008101249482A CN200810124948A CN101328286B CN 101328286 B CN101328286 B CN 101328286B CN 2008101249482 A CN2008101249482 A CN 2008101249482A CN 200810124948 A CN200810124948 A CN 200810124948A CN 101328286 B CN101328286 B CN 101328286B
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- Prior art keywords
- rubber
- mass parts
- tire
- clinch
- rubber combination
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C2015/0614—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead characterised by features of the chafer or clinch portion, i.e. the part of the bead contacting the rim
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10819—Characterized by the structure of the bead portion of the tire
- Y10T152/10846—Bead characterized by the chemical composition and or physical properties of elastomers or the like
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention provides a rubber composition for forming a clinch of a tire, containing a rubber component containing at least one of a natural rubber and an epoxidized natural rubber, and not less than 30 parts by mass of silica and not less than 0.1 part by mass to not more than 10 parts by mass of a quinone diimine compound to 100 parts by mass of the rubber component, and a clinch and a tire formed using the rubber composition.
Description
Technical field
The present invention relates to rubber combination, clinch (clinch) and tire; Particularly relate in order to form the rubber combination of tire clinch; Said composition can reduce the usage quantity from the petroleum resources composition; Processing characteristics when not vulcanizing is good, can form high-wearing feature and high-intensity rubber after the sulfuration, relates to the clinch and the tire that utilize this rubber combination to form.
Background technology
The over half of all-mass of now commercially available tire is to be made up of the composition from petroleum resources.For example; In the radial that general car is used, for the all-mass of tire, as composition from petroleum resources; Viton accounts for twenty percent; Carbon black accounts for twenty percent, and other also contain perfume oil and synthon, the tire all-mass be to constitute more than fifty percent by composition from petroleum resources.
But the environment in recent years problem more and more comes into one's own, and suppresses the stated day crescendoization of Carbon emission.Because petroleum resources are limited, supply reduces year by year, can predict the promotion of oil price in the future, and is limited for the use meeting from the composition of petroleum resources.Again, face the exhausted situation of petroleum resources, the manufacturing that can predict the tire that is made up of the composition from such petroleum resources can be had any problem.
Therefore, just not gazed at (for example, opening the 2004-339287 communique) as the ecological tire that staple forms referring to the spy from the composition (from the composition of resource beyond the oil) of petroleum resources.
Summary of the invention
In above-mentioned ecological tire; From the usage quantity angle of further minimizing from the petroleum resources composition; Even also preferably being used to the one-tenth of resource beyond oil as far as possible, clinch assigns to form; This clinch is the wearing and tearing that produce between wheel rim that reduces tire and steel bead wire, and transition is provided with to the side from the bottom surface of steel bead wire.
For example, the WHITE CARBON BLACK (silica) of having considered to be used to resource beyond oil here substitutes from the carbon black of the petroleum resources weighting agent as the rubber combination that forms clinch.
But, in this case, the problem below having produced, promptly since when not vulcanizing the processing characteristics of rubber combination reduce, thereby the difficulty that is shaped, simultaneously, the wear resisting property of rubber reduces with intensity after the sulfuration, is difficult to be used as the tire clinch.
In view of above-mentioned situation; The object of the present invention is to provide rubber combination; Said composition can reduce the usage quantity from the petroleum resources composition; Processing characteristics when not vulcanizing is good, can form high-wearing feature and high-intensity rubber after the sulfuration, and clinch and the tire that utilizes this rubber combination to form is provided.
The present invention is the rubber combination that is used to form the tire clinch; This rubber combination comprises rubber constituent; Comprise at least a of tree elastomer and epoxy natural rubber in the said rubber constituent; Simultaneously, with respect to the rubber constituent of 100 mass parts, rubber combination contains the above WHITE CARBON BLACK of 30 mass parts and 0.1 mass parts is above, the quinondiimine based compound below 10 mass parts.
In rubber combination of the present invention, as the quinondiimine based compound, the most handy 4-(1, the 3-dimethylbutyl) imino--1-phenylimino benzene.
In rubber combination of the present invention, for the rubber constituent of 100 mass parts, content of carbon black is preferably in below 25 mass parts.
In rubber combination of the present invention, rubber constituent is made up of the mixture of tree elastomer and epoxy natural rubber, and the content of tree elastomer is preferably in more than the 50 quality % of rubber constituent.
Rubber combination of the present invention preferably contains silane coupling agent.
Again, the present invention is the clinch that is formed by above-mentioned arbitrary rubber combination.
Further, the present invention is the tire that utilizes above-mentioned clinch to make.
According to the present invention; Rubber combination can be provided, and said composition can reduce the usage quantity from the petroleum resources composition, and the processing characteristics when not vulcanizing is good; Can form high-wearing feature and high-intensity rubber after the sulfuration, and clinch and the tire that utilizes this rubber combination to form is provided.
Above-mentioned and other purpose of the present invention, characteristic, situation and advantage, but connection with figures understand, be elaborated below relevant the present invention.
Description of drawings
Fig. 1 is the pattern sectional view of half part of upper left quarter of tire one example of the present invention.
Embodiment
Embodiment of the present invention below is described.In accompanying drawing of the present invention, same reference marks is represented with a part or suitable part.
The present inventor is through wholwe-hearted research, and the result finds a kind of rubber combination, and said rubber combination contains rubber constituent; Comprise at least a of tree elastomer and epoxy natural rubber in this rubber constituent; With respect to the rubber constituent of 100 mass parts, also contain above, the quinondiimine based compound below 10 mass parts of above WHITE CARBON BLACK of 30 mass parts and 0.1 mass parts simultaneously, this rubber combination can not only reduce the usage quantity from the petroleum resources composition; And the processing characteristics when not vulcanizing is good; Can also form high-wearing feature and high-intensity rubber after the sulfuration, therefore, when utilizing this rubber combination to make clinch; Can make clinch show outstanding characteristic, thereby accomplish the present invention.
< rubber constituent >
The rubber constituent of using among the present invention is tree elastomer or either party rubber of epoxy natural rubber, or with tree elastomer and the two mixed rubber that mixes of epoxy natural rubber etc.
As stated, utilize at least a rubber constituent that comprises tree elastomer and epoxy natural rubber, therefore, can reduce usage quantity from the petroleum resources composition as rubber constituent.
,, the kind of always knowing can be used here, for example, the general kinds of tire industry such as RSS or TSR can be used as tree elastomer.
As epoxy natural rubber, can use the kind of always knowing, for example, can use commercially available epoxy natural rubber, perhaps tree elastomer is carried out epoxidised rubber clone.
As commercially available epoxy natural rubber, the epoxidation rate that can use Kumplan Guthrie Berhad for example to sell here is that 25% ENR 25 or epoxidation rate are 50% ENR 50 etc.
Again,, can adopt like, glycol chlorohydrin method as tree elastomer is carried out process for epoxidation, direct oxidation method, the alkyl hydroperoxide method is crossed the method for acid system etc.As crossing acid system, can adopt here like, the method that makes the organic peracid of tree elastomer and peroxy acetic acid or peroxyformic acid etc. react.
The epoxidation rate of epoxy natural rubber is advisable more than the % with 5 moles, and better is at 10 moles more than the %.The epoxidation rate especially when 10 moles of % are above, has with the physical properties of tree elastomer to have bigger different tendency at 5 moles more than the %.
The epoxidation rate of epoxy natural rubber is advisable below the % at 80 moles, and better is at 60 moles below the %.The epoxidation rate is at 80 moles below the %; Especially when 60 moles of % are following; Because the inhibition reversion in the time of can vulcanizing; So rubber combination has good consistence after mixing, the processing of rubber combination becomes easily, and the processing characteristics of rubber combination and the performance of tire have the tendency of raising.
So-called epoxidation rate refers to, and the two keys in the rubber are by the ratio (mole %) of the sum of the two keys in this rubber before epoxidised quantity and the epoxidation.
When adopting the two mixed rubber that mixes of tree elastomer and epoxy natural rubber as rubber constituent; The content of tree elastomer is to be advisable more than the 50 quality % that account for the rubber constituent that is made up of tree elastomer and epoxy natural rubber, and better is to account for more than the 60 quality %.The content of tree elastomer accounts for 50 quality % of rubber constituent when above, especially accounts for 60 quality % when above, comprises to utilize the tire of the clinch that rubber combination of the present invention makes to have the tendency that rolling resistance reduces.
If the rubber constituent among the present invention contains at least a of tree elastomer and epoxy natural rubber, containing just like, divinyl rubber (BR), styrene-butadiene rubber(SBR) (SBR), at least a rubber of polyisoprene rubber (IR) or butyl rubber (IIR) etc. is advisable.
< WHITE CARBON BLACK >
Contain in the rubber combination of the present invention with respect to the WHITE CARBON BLACK more than 30 mass parts of the above-mentioned rubber constituent of 100 mass parts.According to such formation, can reduce sooty consumption as weighting agent, therefore, can reduce usage quantity from the composition of petroleum resources, simultaneously, can also obtain the sufficient reinforcing effect that brings by WHITE CARBON BLACK.In addition,, the kind of always knowing can be used, for example anhydrous WHITE CARBON BLACK and/or aqueous WHITE CARBON BLACK etc. can be used as WHITE CARBON BLACK.
Here, from the viewpoint of the sufficient reinforcing effect that obtains to bring by WHITE CARBON BLACK, the content of WHITE CARBON BLACK, with respect to the above-mentioned rubber constituent of 100 mass parts, to be advisable more than 50 mass parts, better is more than 55 mass parts.
And the viewpoint that reduces from the processing characteristics that suppresses rubber combination of the present invention, the content of WHITE CARBON BLACK then, with respect to the above-mentioned rubber constituent of 100 mass parts, to be advisable below 100 mass parts, better is below 95 mass parts.
Here, the nitrogen adsorption specific surface area (N of WHITE CARBON BLACK
2SA) with at 100m
2Be advisable more than/the g, better is at 110m
2More than/the g.Nitrogen adsorption specific surface area (the N of WHITE CARBON BLACK
2SA) at 100m
2When/g is above, especially at 110m
2When/g is above, has the tendency of the sufficient reinforcing effect that can obtain to bring by WHITE CARBON BLACK.
Nitrogen adsorption specific surface area (the N of WHITE CARBON BLACK
2SA) with at 300m
2Be advisable below/the g, better is at 280m
2Below/the g.Nitrogen adsorption specific surface area (the N of WHITE CARBON BLACK
2SA) at 300m
2When/g is following, especially at 280m
2When/g is following, has the dispersed and low febrifacient tendency that improves WHITE CARBON BLACK.
< silane coupling agent >
Rubber combination of the present invention contains silane coupling agent simultaneously and is advisable to contain WHITE CARBON BLACK.As silane coupling agent, can adopt the kind of always knowing here, for example can enumerate two (3-triethoxysilylpropyl) tetrasulfide; Two (2-triethoxy silica ethyl) tetrasulfide, two (3-trimethoxy silicon propyl group) tetrasulfide, two (2-trimethoxy silica ethyl) tetrasulfide, two (3-triethoxysilylpropyl) trisulphide; Two (3-trimethoxy silicon propyl group) trisulphide, two (3-triethoxysilylpropyl) disulphide, two (3-trimethoxy silicon propyl group) disulphide, 3-trimethoxy silicon propyl group-N; N-dimethylamino thiocarbonyl group tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylamino thiocarbonyl group tetrasulfide, 2-triethoxy silica ethyl-N; N-dimethylamino thiocarbonyl group tetrasulfide, 2-trimethoxy silica ethyl-N, N-dimethylamino thiocarbonyl group tetrasulfide; 3-trimethoxy silicon propylbenzene benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzothiazolyl tetrasulfide, methylacrylic acid 3-triethoxysilicane propyl ester monosulphide; Methylacrylic acid 3-trimethoxy silicon propyl ester monosulphide etc. sulfide-based, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane; 2-mercaptoethyl Trimethoxy silane, the sulfydryl system of 2-mercaptoethyl triethoxyl silane etc., vinyltriethoxysilane; The ethene base system of vinyltrimethoxy silane etc., 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane; 3-(2-aminoethyl) aminopropyl triethoxysilane, the amino system of 3-(2-aminoethyl) aminopropyl trimethoxysilane etc., γ-glycidoxy propyl-triethoxysilicane; γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, the glycidoxy system of γ-glycidoxy propyl group methyl dimethoxysilane etc.; 3-nitro propyl trimethoxy silicane, the nitro system of 3-nitro propyl-triethoxysilicane etc., 3-chloropropyl methoxy silane; The 3-chloropropyl triethoxysilane, 2-chloroethyl Trimethoxy silane, the chlorine system of 2-chloroethyl triethoxyl silane etc.Above-mentioned silane coupling agent both can use the use that also can two or morely combine separately.
The content of silane coupling agent, with respect to the WHITE CARBON BLACK of 100 mass parts, more than 4 mass parts, to be advisable, better is more than 8 mass parts.The content of silane coupling agent; With respect to the WHITE CARBON BLACK of 100 mass parts, when 4 mass parts are above, especially when 8 mass parts are above; Can suppress the increase of rubber combination mooney viscosity of the present invention; Can obtain good processing characteristics, simultaneously, have the tendency of the sulfuration rubber abrasive-resistance afterwards that can improve rubber combination of the present invention.
< carbon black >
Also can contain the carbon black of always knowing in the rubber combination of the present invention from petroleum resources.But from reducing the consumption viewpoint from the composition of petroleum resources, with respect to the above-mentioned rubber constituent of 100 mass parts, content of carbon black is to be advisable below 25 mass parts, and better is below 5 mass parts, does not preferably contain carbon black fully.
As carbon black, can adopt the kind of carbon black of always knowing, for example, SAF, ISAF, HAF, FEF etc.
Sooty nitrogen adsorption specific surface area (N
2SA) with at 30m
2Be advisable more than/the g, better is at 50m
2More than/the g.Sooty nitrogen adsorption specific surface area (N
2SA) at 30m
2When/g is above, especially at 50m
2When/g is above, has the tendency of the sufficient reinforcing effect that can obtain to bring by carbon black.
Sooty nitrogen adsorption specific surface area (N
2SA) with at 300m
2Be advisable below/the g, better is at 250m
2Below/the g.Sooty nitrogen adsorption specific surface area (N
2SA) at 300m
2When/g is following, especially at 250m
2When/g is following, has the tendency that improves rubber combination processing characteristics of the present invention.
< quinondiimine based compound >
In the rubber combination of the present invention,, contain the quinondiimine based compound that 0.1 mass parts is above, 10 mass parts are following with respect to the above-mentioned rubber constituent of 100 mass parts.The quinondiimine based compound also has the effect that rubber combination is reduced at mixing mooney viscosity afterwards when having the anti-aging agent effect.
As the quinondiimine based compound, can adopt here like the represented compound of following general formula (I).
[changing I]
In above-mentioned general formula (I), R and R ' represent aryls such as the alicyclic alkyl, phenyl of chain alkylene, cyclohexyl of methyl, ethyl, n-propyl, sec.-propyl etc. etc. etc. respectively independently.In above-mentioned general formula (I), R and R ' can represent same substituting group respectively, also can represent different substituting groups.
As the quinondiimine based compound, preferably in order to the represented 4-of formula (II) (1, the 3-dimethylbutyl) imino--1-phenylimino benzene.
[changing 2]
The content of quinondiimine based compound, with respect to the above-mentioned rubber constituent of 100 mass parts, more than 1 mass parts, to be advisable, better is more than 2 mass parts.The content of quinondiimine based compound with respect to the rubber constituent of 100 mass parts, when 1 mass parts is above, especially when 2 mass parts are above, can make the mooney viscosity of rubber combination of the present invention when not vulcanizing that the tendency of further reduction is arranged.
Again, the content of quinondiimine based compound is with respect to the above-mentioned rubber constituent of 100 mass parts, with even more ideal below 8 mass parts.The content of quinondiimine based compound with respect to the above-mentioned rubber constituent of 100 mass parts, when 8 mass parts are following, can make the rubber surface quinondiimine based compound bloom of rubber combination of the present invention after sulfuration pollute the tendency that rubber has reduction.
< other compositions >
In the rubber combination of the present invention, except above-mentioned composition, can also for example suitably cooperate the wax that tire industry is general, various anti-aging agent, Triple Pressed Stearic Acid, zinc oxide, various compositions such as the vulcanizing agent of Sulfur etc. or various vulcanization accelerators.
< rubber combination >
Rubber combination of the present invention can mix manufacturing with WHITE CARBON BLACK and quinondiimine based compound through will for example containing above-mentioned tree elastomer and at least one side's of epoxy natural rubber rubber constituent.Here, as required, can certainly suitably add the composition of always knowing and mix.
As the blending means that is used to make rubber combination of the present invention, can adopt the blending means of always knowing, for example, adopt the mill of always knowing, Ben Baili formula Banbury mixer, the compounding process of pressurization kneader or continuous mixer etc.After mixing,, can obtain clinch through rubber combination of the present invention is extruded the shape that formation needs with for example forcing machine.
< tire >
The rubber combination of the invention described above through extruding the shape that methods such as processing are processed to stipulate, forms clinch under unvulcanized state.Then, will comprise that each tyre element of the clinch of such formation is configured on the position of regulation, process green tire, make tire of the present invention through the rubber combination that constitutes each parts of green tire is vulcanized again.
Fig. 1 is the pattern sectional view of half part of upper left quarter of this clearly demarcated tire one example.Here, tire 1 has the tyre surface 2 of the landing ground that becomes tire 1, extend from tyre surface 2 two ends along the tire radial inward to constitute tire 1 lateral pair of sidewall 3, and the bead core 5 that is positioned at each sidewall 3 inner end.Set up cord body 6 between the bead core 5,5, simultaneously, in the outside of this cord body 6 and the inboard of tyre surface 2 is provided with the hoop effect and the belt 7 that tyre surface 2 carried out reinforcement.
Cord body 6; For example can form by film; Buried many cords in the film underground, cord is got for example 70 °～90 ° angle for tire equator CO (center of periphery width that makes tire 1 is along the circumferential direction of the tire 1 periphery resulting imaginary line that turns around).Cord body 6 stops through folding is turned on one's side on sidewall 3 outwardly by the inboard of tire axial around bead core 5 after from tyre surface 2 beginnings.
Belt 7 for example can be formed by film, has buried many cords in the film underground, and cord is got the for example angle below 40 ° for tire equator CO.
As required, the string course (not shown) that inhibition belt 7 is peeled off can also be set in the tire 1.The string course here for example can be formed by the film that is embedded with many cords, can string course be set through rolling film spirally in the outside of almost parallel with tire equator CO belt 7.
In tire 1, be formed with the filler in bead core 8 that extends to tire radial outside from bead core 5; Simultaneously; Be provided with air retaining wall 9 in the inboard of cord body 6,3 clinch 4 to the extension of tire radial the inside cover by sidewall 3 and from the sidewall in the outside of the turnover part of cord body 6.Clinch 4 is through formed to rubber combination sulfuration of the present invention.
Tire 1 with said structure can reduce the wheel rim of tire 1 and the abrasion that steel bead wire produces, and this is because clinch 4 is to form with the rubber combination that the present invention is used for tire, so can make clinch 4 have high wear resistance and high-intensity cause.
The tire 1 of said structure so can become the treatment environment, can be tackled the ecological tire of oil supply amount minimizing in the future owing to can suppress the consumption from the petroleum resources composition.
Though tire 1 as shown in Figure 1 is the tire of using as car, the present invention does not limit therewith, goes for for example car usefulness, truck usefulness, motorbus usefulness, the various tires of heavy vehicles.
From suppress from the petroleum resources composition with measuring angle, the one-tenth that preferably also is used to as much as possible beyond the petroleum resources composition of the tire position except clinch 4 assigns to make undoubtedly.
Embodiment
<unvulcanized rubber preparation of compositions >
Formulation shown in Table 1, using (strain) Kobe steel 1.7 l Banbury mixer, natural rubber, epoxidized natural rubber, silica, a silane coupling agent and the quinone diimine compound 130 ℃ kneaded for 2 minutes to obtain a master batch.
Next, the master batch obtained as described above, after a discharge, the (strain) of 1.7 l Kobe Steel will Banbury mixer and sulfur in addition to components other than the vulcanization accelerator added to the master batch obtained as go, kneaded at 130 ℃ for 2 minutes to obtain a kneaded material.
Then, the mixing thing that adopts mill that above-mentioned that kind is obtained, Sulfur and vulcanization accelerator descended mixing 2 minutes at 95 ℃, obtained embodiment 1～3 and comparative example 1～3 unvulcanized rubber compsn separately.Again, to become the numerical value shown in subfields be the mass parts of the use level of the rubber constituent use level of each composition when being 100 mass parts for other of table 1.
[table 1]
(annotating 1) tree elastomer (NR): TSR
(annotating 2) epoxy natural rubber (ENR): ENR25 (the epoxidation rate: 25%) that Kumplan Guthrie Berhad produces
The SBR1502 that (annotating 3) divinyl rubber (BR): JSR (strain) produces
SHOWBLACKN330 (the N that (annotating 4) carbon black: Cabot Japan (strain) produces
2SA:115m
2/ g)
ULTRASIL VN3 (the N that (annotating 5) WHITE CARBON BLACK: Degussa produces
2SA:175m
2/ g)
The Si-69 (two (3-triethoxysilylpropyl) tetrasulfide) that (annotating 6) silane coupling agent: Degussa produces
The Q-FLEX QDI (4-(1, the 3-dimethylbutyl) imino--1-phenylimino benzene) that (annotating 7) quinondiimine based compound: FLEXSYS produces
(annotating 8) wax: the SUNNOC WAX that the emerging chemical industry of imperial palace (strain) is produced
(annotating 9) age resistor: the NOCRAC 6C (N-(1, the 3-dimethylbutyl)-N '-phenyl-p-phenylenediamine (PPD)) that the emerging chemical industry of imperial palace (strain) is produced
(annotating 10) Triple Pressed Stearic Acid: Japanese grease (strain) is produced
(Note 11) Zinc oxide: Mitsui Mining Ye (strain) of zinc white No. 1 produced
(Note 12) Sulfur: Tsurumi Chemical Engineering Ye (strain) produced sulfur powder
(annotating 13) vulcanization accelerator: the NOCCELER-NS (the N-tert-butyl group-2-[4-morpholinodithio base-sulfenamide) that the emerging chemical industry of imperial palace (strain) is produced
< mooney viscosity >
Embodiment 1～3 and comparative example 1～3 each unvulcanized rubber compsn are accordinged to JIS K6300-1 " unvulcanized rubber physical property part 1: the method for asking viscosity and time of scorch with mooney's viscosimeter ", under 130 ℃ condition, measure mooney viscosity.Its result is as shown in table 1.In the table 1, mooney viscosity is to be that 100 o'clock relative value is represented with the mooney viscosity at the unvulcanized rubber compsn of comparative example 1.
In addition, the numerical value on this hurdle of mooney viscosity of table 1 is big more, representes that then mooney viscosity is low more, and processing characteristics is excellent more good.The numerical value on this hurdle of mooney viscosity of table 1 is good greater than the processing characteristics of 80 unvulcanized rubber compsn.
< film processing characteristics >
With roller each unvulcanized rubber compsn of embodiment 1～3 and comparative example 1～3 is carried out compressing tablet, obtain the green compound sheet that each the unvulcanized rubber compsn by embodiment 1～3 and comparative example 1～3 forms.
Through the range estimation on the surface of these green compound sheets being confirmed the shape of green compound sheet.Its result is as shown in table 1.
In addition, in the film processing characteristics hurdle of table 1, confirm that the film that does not have problems such as side cut is decided to be A, processing characteristics is good, and confirming has the film of problems such as side cut then to be decided to be B, and processing characteristics is bad.
< pik (ピ コ) abrasion test >
To as each unvulcanized rubber compsn of the above-mentioned embodiment that obtains 1～3 and comparative example 1～3 vulcanized respectively 30 minutes at 150 ℃, what obtain embodiment 1～3 and comparative example 1～3 respectively vulcanizes adhesive tape.
Then; Embodiment 1～3 that above-mentioned that kind is obtained and comparative example 1～3 respectively vulcanize adhesive tape; According to JIS K6264-2 " vulcanized rubber and thermoplastic elastomer wear resistance ask method-part 2: test method "; On (strain) pik abrasion test instrument that upward the island making is produced, carry out abrasion, measure the abrasion volume that respectively vulcanizes adhesive tape.And, as 100, calculate embodiment 1～3 and comparative example 1～3 sulfuration adhesive tape pik abrasion index separately according to following formula (1) then with the abrasion volume of the sulfuration adhesive tape of comparative example 1.Its result is as shown in table 1.
(pik abrasion index)=100x (the abrasion volume of the sulfuration adhesive tape of comparative example 1)/(the abrasion volume separately of embodiment 1～3 and comparative example 1～3 sulfuration adhesive tape) ... (1)
In addition, the pik abrasion index value of table 1 was greater than 100 o'clock, and is good with the wear resistance of wheel rim.
< tensile test >
To the foregoing description 1～3 and comparative example 1～3 respectively vulcanize adhesive tape, according to JIS K6251 " vulcanized rubber and TPR tensile properties ask method ", carry out tensile test with No. 3 test films of dumbbell shaped.Then, respectively to embodiment 1～3 and comparative example 1～3 respectively vulcanize adhesive tape according to tensile strength (TS) and the elongation (Eb) when cutting off calculate energy of rupture (TS x Eb/2), then, as 100, calculate intensity index by following formula (2) with the energy of rupture of comparative example 1.Its result is as shown in table 1.
(rubbery intensity index)=100x (energy of rupture separately that respectively vulcanizes adhesive tape of embodiment 1～3 and comparative example 1～3)/(energy of rupture of comparative example 1 sulfuration adhesive tape) ... (2)
In addition, the numerical value on the rubbery intensity index hurdle of table 1 is big more, and the expression rubbery intensity is high more, so be not easy jagged.
< evaluation >
Can know from the result shown in the table 1; Comprise at least a of tree elastomer and epoxy natural rubber in the rubber constituent that contains; Simultaneously; With respect to the rubber constituent of 100 mass parts, rubber combination contains the above WHITE CARBON BLACK of 30 mass parts and 0.1 mass parts is above, the rubber combination of the embodiment 1～3 of the quinondiimine based compound below 10 mass parts when not vulcanizing, and do not contain WHITE CARBON BLACK; Only always compare, have the processing characteristics of equal extent as the rubber combination of the comparative example 1 of the rubber combination of clinch with sooty.After the sulfuration, the rubber combination of embodiment 1～3 is compared with the rubber combination of comparative example 1, not only has the pik abrasion index of equal extent, and the rubbery intensity index demonstrates than comparative example 1 better result.
As shown in table 1; The rubber combination of embodiment 1 is compared and can be found out with the rubber combination of comparative example 2; Rubber constituent for 100 mass parts; The rubber combination that contains the embodiment 1 of 4 mass parts quinondiimine based compounds is compared with the rubber combination of the comparative example that does not contain the quinondiimine based compound 2, and mooney viscosity is low, the film good processability.
As shown in table 1, have the rubber combination of the embodiment 1～3 of above-mentioned composition, when not vulcanizing, its mooney viscosity is lower than the rubber combination of the comparative example 3 that does not contain the quinondiimine based compound.
Therefore; Can think according to above result; Because the rubber combination of embodiment 1～3 is in the consumption that suppresses from the petroleum resources composition, the mooney viscosity when not vulcanizing is low, and the film processing characteristics is good; Wear resistance after the sulfuration and intensity are high, so the rubber combination of embodiment 1～3 can be applicable to the formation of tire clinch.
According to the present invention; Can provide in order to form the rubber combination of tire clinch; Said composition can reduce the usage quantity from the petroleum resources composition; Processing characteristics when not vulcanizing is good, can form high-wearing feature and high-intensity rubber combination after the sulfuration, and the clinch and the tire that utilize this rubber combination to form can be provided.
Though carried out detailed explanation with regard to the present invention, these only are some examples, are not limited to this, are to be understood that, explain scope of the present invention according to the scope of claim.
Claims (5)
1. rubber combination that is used to form the tire clinch; This rubber combination contains rubber constituent; Said rubber constituent is the mixture of tree elastomer and epoxy natural rubber, simultaneously, and with respect to the above-mentioned rubber constituent of 100 mass parts; This rubber combination contains the above WHITE CARBON BLACK of 30 mass parts and 0.1 mass parts is above, the quinondiimine based compound below 10 mass parts
Wherein, in said rubber components, the content of said tree elastomer is not less than 50 quality % of said rubber constituent, and
Wherein, said quinondiimine based compound is 4-(1, the 3-dimethylbutyl) imino--1-phenylimino benzene shown in following general formula (II)
2. rubber combination as claimed in claim 1 is characterized by, and for the above-mentioned rubber constituent of 100 mass parts, sooty content is below 25 mass parts.
3. rubber combination as claimed in claim 1 is characterized by, and contains silane coupling agent.
4. clinch that forms by the described rubber combination of claim 1.
5. tire that uses the described clinch of claim 4 to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007160103 | 2007-06-18 | ||
| JP2007160103A JP4467605B2 (en) | 2007-06-18 | 2007-06-18 | Rubber composition, clinch and tire |
| JP2007-160103 | 2007-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101328286A CN101328286A (en) | 2008-12-24 |
| CN101328286B true CN101328286B (en) | 2012-02-29 |
Family
ID=39952266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101249482A Expired - Fee Related CN101328286B (en) | 2007-06-18 | 2008-06-18 | Rubber composition, clinch, and tire |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20080308207A1 (en) |
| EP (1) | EP2006122B1 (en) |
| JP (1) | JP4467605B2 (en) |
| KR (1) | KR100976834B1 (en) |
| CN (1) | CN101328286B (en) |
| DE (1) | DE602008003258D1 (en) |
| RU (1) | RU2391220C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5346390B2 (en) * | 2011-05-27 | 2013-11-20 | 住友ゴム工業株式会社 | Pneumatic tire |
| CN103131056A (en) * | 2011-11-29 | 2013-06-05 | 陈亚洲 | Light color traceless environment-friendly solid tire and manufacturing technology thereof |
| CN105330899B (en) * | 2015-12-14 | 2018-08-07 | 中国热带农业科学院农产品加工研究所 | A kind of epoxy natural rubber coating modification white carbon and preparation method thereof and rubber material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278840A (en) * | 1997-10-20 | 2001-01-03 | 弗莱克斯塞思美国有限合伙公司 | Quinone diimine as a rubber additive |
| CN1481415A (en) * | 2000-12-20 | 2004-03-10 | �����ɷ� | Silica-filled rubbers comprising quinone dimine |
| CN1821292A (en) * | 2005-02-14 | 2006-08-23 | 住友橡胶工业株式会社 | Rubber composition and tire comprising thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0585860A (en) * | 1991-09-30 | 1993-04-06 | Kansai Shin Gijutsu Kenkyusho:Kk | Transparent uniform organic and inorganic complex material |
| US5396940A (en) * | 1993-09-17 | 1995-03-14 | The Goodyear Tire & Rubber Company | Sulfur cured rubber composition containing epoxidized natural rubber and silica filler |
| US6376728B1 (en) * | 2000-06-20 | 2002-04-23 | Hercules Incorporated | Method, composition and mixture for inhibiting monomer polymerization |
| KR100805489B1 (en) | 2000-12-20 | 2008-02-20 | 플렉시스 비.브이. | Silica-Filled Rubber Containing Quinone Diimine |
| US6845797B2 (en) * | 2001-10-12 | 2005-01-25 | Bridgestone Corporation | Tire compositions comprising epoxidized natural rubber and a functionalized polyolefin |
| JP4384873B2 (en) | 2003-05-13 | 2009-12-16 | 住友ゴム工業株式会社 | Rubber composition for bead apex and pneumatic tire using the same |
| JP4088260B2 (en) * | 2004-03-03 | 2008-05-21 | 住友ゴム工業株式会社 | Rubber composition for clinch and pneumatic tire using the same |
| JP4805584B2 (en) * | 2005-01-21 | 2011-11-02 | 住友ゴム工業株式会社 | Rubber composition for tread and tire comprising the same |
| JP4628888B2 (en) * | 2005-06-29 | 2011-02-09 | 住友ゴム工業株式会社 | tire |
| US20070135895A1 (en) | 2005-12-13 | 2007-06-14 | Robert Burgermeister | Polymeric stent having modified molecular structures in both the hoops and selected segments of the flexible connectors |
-
2007
- 2007-06-18 JP JP2007160103A patent/JP4467605B2/en not_active Expired - Fee Related
-
2008
- 2008-06-09 US US12/155,721 patent/US20080308207A1/en not_active Abandoned
- 2008-06-11 EP EP08010618A patent/EP2006122B1/en not_active Ceased
- 2008-06-11 DE DE602008003258T patent/DE602008003258D1/en active Active
- 2008-06-17 RU RU2008125713/02A patent/RU2391220C2/en not_active IP Right Cessation
- 2008-06-17 KR KR1020080056956A patent/KR100976834B1/en not_active IP Right Cessation
- 2008-06-18 CN CN2008101249482A patent/CN101328286B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278840A (en) * | 1997-10-20 | 2001-01-03 | 弗莱克斯塞思美国有限合伙公司 | Quinone diimine as a rubber additive |
| CN1481415A (en) * | 2000-12-20 | 2004-03-10 | �����ɷ� | Silica-filled rubbers comprising quinone dimine |
| CN1821292A (en) * | 2005-02-14 | 2006-08-23 | 住友橡胶工业株式会社 | Rubber composition and tire comprising thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2391220C2 (en) | 2010-06-10 |
| RU2008125713A (en) | 2009-12-27 |
| CN101328286A (en) | 2008-12-24 |
| JP2008308639A (en) | 2008-12-25 |
| KR20080111406A (en) | 2008-12-23 |
| KR100976834B1 (en) | 2010-08-20 |
| US20080308207A1 (en) | 2008-12-18 |
| EP2006122B1 (en) | 2010-11-03 |
| EP2006122A1 (en) | 2008-12-24 |
| JP4467605B2 (en) | 2010-05-26 |
| DE602008003258D1 (en) | 2010-12-16 |
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